Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid.

Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H2 activation using iPr3SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr3Sn·base}{Al[OC(CF3)3]4} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H2 activation and hence resolve any mechanistic roles for OTf- in the iPr3SnOTf-mediated pathway.

A New Mode of Chemical Reactivity for Metal-Free Hydrogen Activation by Lewis Acidic Boranes.

We herein explore whether tris(aryl)borane Lewis acids are capable of cleaving H2 outside of the usual Lewis acid/base chemistry described by the concept of frustrated Lewis pairs (FLPs). Instead of a Lewis base we use a chemical reductant to generate stable radical anions of two highly hindered boranes: tris(3,5-dinitromesityl)borane and tris(mesityl)borane. NMR spectroscopic characterization reveals that the corresponding borane radical anions activate (cleave) dihydrogen, whilst EPR spectroscopic characterization, supported by computational analysis, reveals the intermediates along the hydrogen activation pathway. This radical-based, redox pathway involves the homolytic cleavage of H2 , in contrast to conventional models of FLP chemistry, which invoke a heterolytic cleavage pathway. This represents a new mode of chemical reactivity for hydrogen activation by borane Lewis acids.

Direct Reductive Amination of Carbonyl Compounds Catalyzed by a Moisture Tolerant Tin(IV) Lewis Acid.

Despite the ever-broadening applications of main-group 'frustrated Lewis pair' (FLP) chemistry to both new and established reactions, their typical intolerance of water, especially at elevated temperatures (>100 °C), represents a key barrier to their mainstream adoption. Herein we report that FLPs based on the Lewis acid iPr3SnOTf are moisture tolerant in the presence of moderately strong nitrogenous bases, even under high temperature regimes, allowing them to operate as simple and effective catalysts for the reductive amination of organic carbonyls, including for challenging bulky amine and carbonyl substrate partners.

Base-induced reversible H2 addition to a single Sn(ii) centre.

A range of amines catalyse the oxidative addition (OA) of H2 to [(Me3Si)2CH]2Sn (1), forming [(Me3Si)2CH]2SnH2 (2). Experimental and computational studies point to 'frustrated Lewis pair' mechanisms in which 1 acts as a Lewis acid and involve unusual late transition states; this is supported by the observation of a kinetic isotope effect for Et3N. When DBU is used the energetics of H2 activation are altered, allowing an equilibrium between 1, 2 and adduct [1·DBU] to be established, thus demonstrating reversible oxidative addition/reductive elimination (RE) of H2 at a single main group centre.

Hydrogen activation using a novel tribenzyltin Lewis acid.

Over the last decade there has been an explosion in the reactivity and applications of frustrated Lewis pair (FLP) chemistry. Despite this, the Lewis acids (LAs) in these transformations are often boranes, with heavier p-block elements receiving surprisingly little attention. The novel LA Bn3SnOTf (1) has been synthesized from simple, inexpensive starting materials and has been spectroscopically and structurally characterized. Subtle modulation of the electronics at the tin centre has led to an increase in its Lewis acidity in comparison with previously reported R3SnOTf LAs, and has facilitated low temperature hydrogen activation and imine hydrogenation. Deactivation pathways of the R3Sn+ LA core have also been investigated.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

Versatile Catalytic Hydrogenation Using A Simple Tin(IV) Lewis Acid.

Despite the rapid development of frustrated Lewis pair (FLP) chemistry over the last ten years, its application in catalytic hydrogenations remains dependent on a narrow family of structurally similar early main-group Lewis acids (LAs), inevitably placing limitations on reactivity, sensitivity and substrate scope. Herein we describe the FLP-mediated H2 activation and catalytic hydrogenation activity of the alternative LA iPr3 SnOTf, which acts as a surrogate for the trialkylstannylium ion iPr3 Sn+ , and is rapidly and easily prepared from simple, inexpensive starting materials. This highly thermally robust LA is found to be competent in the hydrogenation of a number of different unsaturated functional groups (which is unique to date for main-group FLP LAs not based on boron), and also displays a remarkable tolerance to moisture.